WO2018139136A1 - Copolymère de polycarbonate - Google Patents

Copolymère de polycarbonate Download PDF

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Publication number
WO2018139136A1
WO2018139136A1 PCT/JP2017/046163 JP2017046163W WO2018139136A1 WO 2018139136 A1 WO2018139136 A1 WO 2018139136A1 JP 2017046163 W JP2017046163 W JP 2017046163W WO 2018139136 A1 WO2018139136 A1 WO 2018139136A1
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Prior art keywords
structural unit
parts
polycarbonate copolymer
formula
polycarbonate resin
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PCT/JP2017/046163
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English (en)
Japanese (ja)
Inventor
常守　秀幸
山中　克浩
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帝人株式会社
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Application filed by 帝人株式会社 filed Critical 帝人株式会社
Priority to JP2018564174A priority Critical patent/JP6684931B2/ja
Priority to EP17894197.7A priority patent/EP3575340B1/fr
Priority to CN201780084671.2A priority patent/CN110225934B/zh
Priority to US16/480,019 priority patent/US20190390006A1/en
Publication of WO2018139136A1 publication Critical patent/WO2018139136A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/22—General preparatory processes using carbonyl halides
    • C08G64/24—General preparatory processes using carbonyl halides and phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters

Definitions

  • the present invention relates to a polycarbonate resin (polycarbonate copolymer) capable of suppressing polymer degradation under conditions exposed to a basic environment containing an amine.
  • the present invention also relates to a polycarbonate resin molded article (sheet, film, etc.) excellent in amine resistance suitable for production of automobile interior parts.
  • the present invention relates to an automotive interior part having excellent scratch resistance, impact resistance, heat resistance, and amine resistance made of a polycarbonate resin having a specific structural unit.
  • the polyurethane foam is produced from polyol and polyisocyanate as main raw materials, and is foamed while being mixed with a foaming agent, a foam stabilizer, a catalyst, a colorant, and the like.
  • Polyurethane foam is widely used in the automotive field, particularly for seat cushions, door trims, headrests, armrests, handles, floor and ceiling sound absorbing and damping materials, cushioning materials, sun visors, and the like.
  • the tertiary amine compound used as a catalyst is an indispensable substance in the reaction of polyurethane foam into resins and foaming / swelling reactions.
  • the amine catalyst gradually volatilizes from the polyurethane foam after production, causing discoloration and whitening of other interior parts.
  • a polycarbonate resin having bisphenol A as a structural unit is known as a polycarbonate resin.
  • This polycarbonate resin is excellent in transparency, impact resistance, heat resistance, and dimensional stability. For this reason, they are used as engineering plastics in a wide range of fields such as electrical and electronic equipment casings, automobile interior and exterior parts, building materials, furniture, musical instruments, and miscellaneous goods.
  • specific gravity is low and weight reduction is possible and it is excellent in productivity, it is used for windows, such as a motor vehicle.
  • seat and film using a polycarbonate resin are widely used as various display apparatuses and protection components of a motor vehicle interior by performing additional secondary processes, such as a coating process, a laminated body, and surface modification.
  • a polycarbonate resin that has not been subjected to a coating treatment has a problem that when exposed to a basic environment containing an amine, the polymer is decomposed and the surface of the molded product is whitened.
  • polycarbonates and copolycarbonates whose structural units are 2,2-bis (4-hydroxy-3-methylphenyl) propane (for example, Patent Documents 2 to 6).
  • the polycarbonate resin has an excellent surface hardness, but has a problem that heat resistance is inferior to that of a polycarbonate resin having bisphenol A as a constituent unit.
  • polycarbonates and copolycarbonates containing 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane as structural units are known (for example, Patent Documents 7 to 8). ).
  • This polycarbonate resin is excellent in surface hardness and heat resistance, but is a resin composition with a polycarbonate resin having bisphenol A as a structural unit, and is inferior in amine resistance. Therefore, there is still no polycarbonate resin excellent in scratch resistance, impact resistance, heat resistance and amine resistance.
  • JP 2009-500195 A Japanese Patent Application Laid-Open No. 64-069625 JP 08-183852 A Japanese Patent Laid-Open No. 08-034846 JP 2002-117580 A JP 2003-252978 A Japanese Unexamined Patent Publication No. 2016-141721 Japanese Unexamined Patent Publication No. 2016-141722
  • An object of the present invention is to provide a polycarbonate resin excellent in scratch resistance, impact resistance, heat resistance and amine resistance. Another object of the present invention is to provide a polycarbonate resin molded article suitable for automobile interior parts.
  • R 1 and R 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms which may contain an aromatic group, or a halogen atom.
  • R 3 and R 4 are each independently an alkyl group having 1 to 6 carbon atoms or a halogen atom.
  • X is a single bond, a substituted or unsubstituted alkylene group, or a substituted group. Or an unsubstituted alkanediyl group, a sulfur atom, or an oxygen atom.
  • W represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkanediyl group, a sulfur atom, or an oxygen atom.
  • the proportion of the structural unit (A) in all the structural units is 5 to 25 mol%, the proportion of the structural unit (B) is 35 to 60 mol%, and the structural unit (C) A polycarbonate copolymer having a ratio of 30 to 50 mol%.
  • R 1 and R 2 in formula (1) are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R 3 and R 4 in formula (2) are each independently the number of carbon atoms
  • An alkyl group having 1 to 6 and X is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkanediyl group having 1 to 10 carbon atoms
  • W in the formula (3) is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkanediyl group having 1 to 10 carbon atoms.
  • (Configuration 4) 4. The polycarbonate copolymer according to any one of items 1 to 3, wherein the Rockwell hardness measured by a Rockwell hardness meter (M scale) is 95 to 120 in accordance with JIS K7202-2.
  • (Configuration 8) 8. The polycarbonate copolymer according to any one of items 1 to 7, wherein the structural unit (B) is a structural unit derived from 2,2-bis (4-hydroxy-3-methylphenyl) propane.
  • the polycarbonate resin of the present invention and a molded product made thereof are excellent in amine resistance, scratch resistance, heat resistance and impact resistance, and are therefore suitably used for automobile interior parts. Therefore, the industrial effects that it plays are exceptional.
  • the polycarbonate resin of the present invention has (A) the following formula (1) as a main structural unit.
  • R 1 and R 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms which may contain an aromatic group, or a halogen atom.
  • R 3 and R 4 are each independently an alkyl group having 1 to 6 carbon atoms or a halogen atom.
  • X is a single bond, a substituted or unsubstituted alkylene group, or a substituted group. Or an unsubstituted alkanediyl group, a sulfur atom, or an oxygen atom.
  • W represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkanediyl group, a sulfur atom, or an oxygen atom.
  • main refers to 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, more preferably 95 mol% or more, among 100 mol% of all carbonate structural units excluding terminals. The ratio is preferably 100 mol%.
  • R 1 and R 2 are each independently preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom. .
  • dihydric phenol from which the structural unit (A) is derived examples include 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, 7,7′-dimethyl-6, 6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, 7,7′-diphenyl-6,6′-dihydroxy-3,3,3 ′, 3′-tetra And methyl-1,1′-spirobiindane.
  • the most preferred dihydric phenol is 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane.
  • the ratio of the structural unit (A) to the total structural unit is 5 to 25 mol%.
  • the proportion of the structural unit (A) exceeds 25 mol%, the heat resistance is improved, but the moldability is inferior, which is not preferable.
  • the proportion of the structural unit (A) is less than 5 mol%, the heat resistance and scratch resistance are inferior, which is not preferable.
  • R 3 and R 4 are preferably each independently an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. More preferably, it is a group.
  • X is preferably a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkanediyl group having 1 to 10 carbon atoms, more preferably a single bond.
  • the alkanediyl group is preferably a propane-2,2-diyl group.
  • dihydric phenol examples include 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter sometimes referred to as bisphenol C), 2,2-bis (4 -Hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-t-butyl-4-hydroxyphenyl) propane, and the like.
  • bisphenol C 2,2-bis (4-hydroxy-3-methylphenyl) propane
  • 2,2-bis (4 -Hydroxy-3-isopropylphenyl) propane 2,2-bis (3-t-butyl-4-hydroxyphenyl) propane
  • the most preferred dihydric phenol is bisphenol C.
  • the ratio of the structural unit (B) to the total structural unit is 35 to 60 mol%, preferably 40 to 55 mol%.
  • the proportion of the structural unit (B) exceeds 60 mol%, the impact resistance and heat resistance are inferior.
  • the proportion of the structural unit (B) is less than 35 mol%, the amine resistance and scratch resistance are inferior.
  • W is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted carbon atom having 1 to 10 carbon atoms.
  • alkanediyl groups more preferably a single bond, an unsubstituted alkylene group having 1 to 5 carbon atoms, or an unsubstituted alkanediyl group having 1 to 5 carbon atoms, An unsubstituted alkanediyl group having 1 to 5 carbon atoms is preferred.
  • the alkanediyl group is preferably a propane-2,2-diyl group.
  • Examples of the dihydric phenol for deriving the structural unit (C) include 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes referred to as bisphenol A), 4,4′-dihydroxy-1,1- Biphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl thioether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 1,1- Bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 4, 4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydro Shifeniru) octane, 1,1-bis (4-hydroxyphenyl) decane and the like
  • the ratio of the structural unit (C) to the total structural unit is 30 to 50 mol%, preferably 35 to 45 mol%, more preferably 40 to 45 mol%.
  • the proportion of the structural unit (C) exceeds 50 mol%, scratch resistance and amine resistance are inferior, which is not preferable.
  • the proportion of the structural unit (C) is less than 30 mol%, the impact resistance is inferior, which is not preferable.
  • the dihydric phenol for deriving the structural units other than the structural units (A), (B) and (C) 2,6-dihydroxynaphthalene, hydroquinone, resorcinol, an alkyl group having 1 to 3 carbon atoms is preferable.
  • Resorcinol substituted with 3- (4-hydroxyphenyl) -1,1,3-trimethylindan-5-ol, 1- (4-hydroxyphenyl) -1,3,3-trimethylindan-5-ol, 1-methyl-1,3-bis (4-hydroxyphenyl) -3-isopropylcyclohexane, 1-methyl-2- (4-hydroxyphenyl) -3- [1- (4-hydroxyphenyl) isopropyl] cyclohexane, 1 , 6-bis (4-hydroxyphenyl) -1,6-hexanedione and the like.
  • the polycarbonate resin of the present invention is obtained by reacting a dihydric phenol with a carbonate precursor.
  • the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.
  • interfacial polycondensation a terminal stopper of a monohydric phenol is usually used.
  • the branched polycarbonate which polymerized the trifunctional component may be sufficient, and also the copolymer polycarbonate which copolymerized aliphatic dicarboxylic acid, aromatic dicarboxylic acid, and a vinyl-type monomer may be sufficient.
  • the reaction is usually performed in the presence of an acid binder and a solvent.
  • an acid binder for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used.
  • the solvent for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used.
  • a catalyst such as a tertiary amine or a quaternary ammonium salt can be used.
  • the reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours.
  • a transesterification reaction using a carbonic acid diester as a carbonate precursor is a method in which an aromatic dihydroxy component in a predetermined ratio is heated and stirred with a carbonic acid diester in an inert gas atmosphere to distill the resulting alcohol or phenol. Is done.
  • the reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C.
  • the reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning.
  • the catalyst normally used for transesterification can also be used.
  • Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.
  • monofunctional phenols are commonly used as end terminators for molecular weight control, particularly in reactions using phosgene as the carbonate precursor. Moreover, since the terminal of the obtained polycarbonate resin is blocked with a group based on monofunctional phenols, it is excellent in thermal stability as compared with those not.
  • Specific examples of the monofunctional phenols include, for example, phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, Examples thereof include p-cumylphenol, isooctylphenol, and p-long chain alkylphenol.
  • the polycarbonate resin of the present invention can be copolymerized with an aliphatic diol as necessary.
  • aliphatic diols isosorbide: 1,4: 3,6-dianhydro-D-sorbitol, tricyclodecane dimethanol, 4,8-bis (hydroxymethyl) tricyclodecane, cis / trans-2,2,4, 4-tetramethylcyclobutane-1,3-diol, cis / trans-1,4-cyclohexanedimethanol, cis / trans-1,4-bis (hydroxymethyl) cyclohexane, cyclohex-1,4-ylenedimethanol, trans -1,4-cyclohexanedimethanol, trans-1,4-bis (hydroxymethyl) cyclohexane, cis-1,4-cyclohexanedimethanol, cis-1,4-bis (hydroxymethyl) cyclohexane, cis-1,4-cyclohexan
  • the polycarbonate resin of this invention can copolymerize a fatty acid as needed.
  • fatty acids 1,10-dodecanedioic acid, adipic acid, hexanedioic acid, isophthalic acid, 1,3-benzenedicarboxylic acid, terephthalic acid, 1,4-benzenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 3- Examples include hydroxybenzoic acid, and 4-hydroxybenzoic acid.
  • the polycarbonate resin of the present invention contains a polyester carbonate obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid.
  • the aliphatic bifunctional carboxylic acid is preferably ⁇ , ⁇ -dicarboxylic acid.
  • the aliphatic difunctional carboxylic acid include, for example, linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosanedioic acid, and cyclohexane.
  • Preferred are alicyclic dicarboxylic acids such as dicarboxylic acids. These carboxylic acids may be copolymerized as long as the purpose is not impaired.
  • the polycarbonate resin of this invention can also copolymerize the structural unit containing a polyorganosiloxane unit as needed.
  • the polycarbonate resin of the present invention can be made into a branched polycarbonate by copolymerizing structural units containing a trifunctional or higher polyfunctional aromatic compound as necessary.
  • the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate include 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2,2,4,6-trimethyl- 2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1 -Tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, and 4- ⁇ 4- [1,1-bis ( Preferred examples include trisphenol such as 4-hydroxyphenyl) ethyl] benzene ⁇ - ⁇ , ⁇ -dimethylbenzylphenol.
  • 1,1,1-tris (4-hydroxyphenyl) ethane is preferred.
  • the structural unit derived from such a polyfunctional aromatic compound is preferably 0.03 to 1.5 mol%, more preferably 0.1% in a total of 100 mol% with respect to structural units from other divalent components. It is ⁇ 1.2 mol%, particularly preferably 0.2 to 1.0 mol%.
  • the branched structural unit is not only derived from a polyfunctional aromatic compound but also derived from a side reaction that occurs during the polymerization reaction by the melt transesterification method without using a polyfunctional aromatic compound. May be.
  • the ratio of the branched structure can be calculated by 1 H-NMR measurement.
  • the polycarbonate resin of the present invention has a viscosity average molecular weight (Mv) of preferably 15,000 to 40,000, more preferably 16,000 to 35,000, still more preferably 18,000 to 30, 000.
  • Mv viscosity average molecular weight
  • a polycarbonate resin having a viscosity average molecular weight of less than 15,000 may not provide practically sufficient toughness and crack resistance (impact resistance).
  • a polycarbonate resin having a viscosity average molecular weight of more than 40,000 is inferior in versatility because it requires a high molding temperature or requires a special molding method, and further increases the melt viscosity, thereby increasing the injection speed. The dependency is likely to increase, and the yield may decrease due to poor appearance or the like.
  • the viscosity average molecular weight Mv is calculated from the obtained specific viscosity ( ⁇ SP ) by the following formula.
  • the polycarbonate resin (polycarbonate copolymer) of the present invention is a function known per se such as a mold release agent, a heat stabilizer, an ultraviolet absorber, a flow modifier, and an antistatic agent, as long as the effects of the present invention are not impaired. It can be set as the resin composition containing the agent.
  • the polycarbonate resin of the present invention may be used in combination with a mold release agent as long as the effects of the present invention are not impaired.
  • the release agent include fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymer, etc., which can be modified with a functional group-containing compound such as acid modification), fluorine compounds (polyethylene And fluorine oil represented by fluoroalkyl ether), paraffin wax, beeswax and the like.
  • fatty acid esters are preferred from the standpoints of availability, releasability and transparency.
  • the ratio of the release agent is preferably 0.005 to 0.5 parts by weight, more preferably 0.007 to 0.4 parts by weight, and still more preferably 0.01 to 0.4 parts by weight with respect to 100 parts by weight of the polycarbonate resin. 0.3 parts by weight.
  • Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids.
  • Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol.
  • the carbon number of the alcohol is preferably in the range of 3 to 32, more preferably in the range of 5 to 30.
  • Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol.
  • polyhydric alcohols examples include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol.
  • a polyhydric alcohol is more preferable.
  • the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms.
  • the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid, And saturated aliphatic carboxylic acids such as docosanoic acid (behenic acid).
  • aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid and cetreic acid.
  • aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable.
  • saturated aliphatic carboxylic acids are preferred. Since such aliphatic carboxylic acids are usually produced from natural fats and oils such as animal fats (such as beef tallow and pork fat) and vegetable fats and oils (such as palm oil), these aliphatic carboxylic acids are usually carbon.
  • the acid value in the fatty acid ester is preferably 20 or less (can take substantially 0). However, in the case of all esters (full esters), it is preferable to contain at least free fatty acids in order to improve releasability. In this respect, the acid value in the full esters is preferably in the range of 3 to 15.
  • the iodine value of the fatty acid ester is preferably 10 or less (can take substantially 0).
  • the aforementioned fatty acid ester may be either a partial ester or a full ester. From the viewpoint of better releasability and durability, partial esters are preferable, and glycerol monoester is particularly preferable.
  • the glycerin monoester is mainly composed of glycerin and a fatty acid monoester. Suitable fatty acids include saturated fatty acids such as stearic acid, palmitic acid, behenic acid, arachidic acid, montanic acid and lauric acid, and unsaturated fatty acids such as oleic acid, linoleic acid and sorbic acid.
  • the partial ester preferably has a sodium metal content of less than 20 ppm, more preferably less than 5 ppm, and even more preferably less than 1 ppm.
  • the fatty acid partial ester having a sodium metal content of less than 1 ppm can be produced by producing the fatty acid partial ester by an ordinary method and then purifying it by molecular distillation or the like.
  • the distillation temperature is 120 to 150 ° C. and the vacuum is 0.01 to 0.03 kPa.
  • polyhydric alcohol such as glycerin.
  • a high-purity fatty acid partial ester is obtained as a distillate using a centrifugal molecular distillation apparatus under the conditions of a distillation temperature of 160 to 230 ° C. and a degree of vacuum of 0.01 to 0.2 Torr.
  • Sodium metal can be removed as a distillation residue.
  • a fatty acid partial ester having a lower sodium metal content By subjecting the resulting distillate to repeated molecular distillation, it is possible to further increase the purity and obtain a fatty acid partial ester having a lower sodium metal content. It is also important to prevent the contamination of the sodium metal component from the external environment by thoroughly washing the inside of the molecular distillation apparatus by an appropriate method in advance and improving airtightness.
  • a fatty acid ester is available from a specialist (for example, Riken Vitamin Co., Ltd.).
  • Phosphorous stabilizers The polycarbonate resin of the present invention is preferably further blended with various phosphorus stabilizers mainly for the purpose of improving the thermal stability during the molding process.
  • phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof.
  • phosphorus stabilizers include tertiary phosphines.
  • phosphite compound for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite,
  • Still other phosphite compounds that react with dihydric phenols and have a cyclic structure can be used.
  • 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite 2,2′-methylenebis (4,6-di-tert-Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite
  • 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and the like.
  • phosphate compound examples include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.
  • Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi.
  • tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferable.
  • Tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite are more preferred.
  • Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.
  • Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.
  • Tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl.
  • Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine.
  • a particularly preferred tertiary phosphine is triphenylphosphine.
  • the phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphite compounds or phosphonite compounds are preferable.
  • Hindered phenol stabilizer (antioxidant)
  • the polycarbonate resin of the present invention can be blended with a hindered phenol stabilizer mainly for the purpose of improving the heat stability during the molding process and the heat aging resistance.
  • hindered phenol stabilizers include, for example, ⁇ -tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl- ⁇ - (4′-hydroxy-3 ′, 5′-di-tert-butylfel ) Propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- ( N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert
  • the amount of the above (ii) phosphorus stabilizer and / or (iii) hindered phenol antioxidant is preferably 0.0001 to 1 part by weight, more preferably 0, per 100 parts by weight of the polycarbonate resin. 0.001 to 0.5 parts by weight, more preferably 0.005 to 0.1 parts by weight. It is difficult to obtain a good stabilizing effect when the stabilizer is too small than the above range, and when it is too much beyond the above range, the physical properties of the material may be deteriorated or the mold may be contaminated during molding. There is.
  • an antioxidant other than the hindered phenol antioxidant can be used as appropriate.
  • examples of such other antioxidants include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), and glycerol-3-stearyl thiopropionate.
  • the amount of these other antioxidants used is preferably 0.001 to 0.05 parts by weight with respect to 100 parts by weight of the polycarbonate resin.
  • the polycarbonate used in the present invention may contain an ultraviolet absorber.
  • the ultraviolet absorber include benzophenone-based compounds such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxy.
  • Benzophenone 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydrate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5- Benzoyl-4-hydroxy-2-methoxy Phenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone and the like.
  • ultraviolet absorber examples include those in the benzotriazole series such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2 -(2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [ 4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzo Triazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazo 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-
  • a copolymer of 2- (2′-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and a vinyl monomer copolymerizable with the monomer 2- (2′-hydroxy-5-
  • examples thereof include polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as a copolymer of (acryloxyethylphenyl) -2H-benzotriazole and a vinyl monomer copolymerizable with the monomer.
  • the ultraviolet absorber examples include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4) in the hydroxyphenyl triazine series. , 6-Diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxy Phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2- Yl) -5-butyloxyphenol and the like.
  • phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is Examples of the compound are phenyl groups.
  • the ultraviolet absorber specifically, in the cyclic imino ester type, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) ) Bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one) and the like.
  • the ultraviolet absorber specifically, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2- Examples include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.
  • the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, whereby the ultraviolet-absorbing monomer and / or the light-stable monomer having a hindered amine structure, and an alkyl (meth) acrylate.
  • Preferred examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic iminoester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylate.
  • benzotriazole and hydroxyphenyltriazine are preferable in terms of ultraviolet absorption ability.
  • cyclic imino ester and cyanoacrylate are preferable.
  • the content of the ultraviolet absorber is 0.01 to 2 parts by weight, preferably 0.03 to 2 parts by weight, more preferably 0.04 to 1 part by weight, and still more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the polycarbonate resin. 05 to 0.5 parts by weight.
  • the polycarbonate resin of the present invention can contain a fluid modifier as long as the effects of the present invention are not impaired.
  • Such flow modifiers include styrene oligomers, polycarbonate oligomers (including highly branched, hyperbranched and cyclic oligomer types), polyalkylene terephthalate oligomers (including highly branched, hyperbranched and cyclic oligomer types)
  • Preferred examples include branched and hyperbranched aliphatic polyester oligomers, terpene resins, and polycaprolactone.
  • Such a flow modifier is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, still more preferably 2 to 15 parts by weight per 100 parts by weight of the polycarbonate resin.
  • Polycaprolactone is particularly preferable, and the composition ratio is particularly preferably 2 to 7 parts by weight per 100 parts by weight of the polycarbonate resin.
  • the molecular weight of polycaprolactone is 1,000 to 70,000 in terms of number average molecular weight, preferably 1,500 to 40,000, more preferably 2,000 to 30,000, and 2,500 to 15,000. Further preferred.
  • the polycarbonate resin of the present invention can contain an antistatic agent for the main purpose of improving antistatic properties.
  • an antistatic agent for the main purpose of improving antistatic properties.
  • sulfonic acid phosphonium salts, phosphite esters, caprolactone-based polymers, and the like can be used, and sulfonic acid phosphonium salts are preferably used.
  • phosphonium sulfonates include tetrabutylphosphonium dodecylsulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tributyloctylphosphonium dodecylbenzenesulfonate, tetraoctylphosphonium dodecylbenzenesulfonate, tetraethylphosphonium octadecylbenzenesulfonate, dibutyl Examples thereof include tributylmethylphosphonium benzenesulfonate, triphenylphosphonium dibutylnaphthylsulfonate, and trioctylmethylphosphonium diisopropylnaphthylsulfonate.
  • the amount of the antistatic agent is preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 3.0 parts by weight, still more preferably 0.3 to 2.0 parts by weight based on 100 parts by weight of the polycarbonate resin. Part by weight, particularly preferably 0.5 to 1.8 parts by weight is blended.
  • the amount is 0.1 parts by weight or more, an antistatic effect is obtained, and when the amount is 5.0 parts by weight or less, the transparency and mechanical strength are excellent, and silver or peeling does not occur on the surface of the molded product, and the appearance is hardly caused.
  • the polycarbonate resin of the present invention can contain various additives such as a bluing agent, a fluorescent dye, a flame retardant, and a dye / pigment. These can be appropriately selected and contained as long as the effects of the present invention are not impaired.
  • the bluing agent preferably comprises 0.05 to 3.0 ppm (weight ratio) in the polycarbonate resin. Representative examples of bluing agents include Macrolex Violet B and Macrolex Blue RR from Bayer, and Polysynthrene Blue RLS from Clariant.
  • fluorescent dyes include coumarin fluorescent dyes, benzopyran fluorescent dyes, perylene fluorescent dyes, anthraquinone fluorescent dyes, thioindigo fluorescent dyes, xanthene fluorescent dyes, and xanthone fluorescent dyes. And thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes.
  • the blending amount of the fluorescent dye (including the fluorescent brightening agent) is preferably 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the polycarbonate resin.
  • the flame retardant examples include sulfonic acid metal salt flame retardants, halogen-containing compound flame retardants, phosphorus-containing compound flame retardants, and silicon-containing compound flame retardants. Among these, a sulfonic acid metal salt flame retardant is preferable.
  • the flame retardant content is preferably 0.01 to 1 part by weight, more preferably 0.05 to 1 part by weight, based on 100 parts by weight of the polycarbonate resin.
  • Various additives can be added to the polycarbonate resin (polycarbonate copolymer) of the present invention to produce a resin composition.
  • a method of adding an additive or the like to the polycarbonate resin of the present invention is not particularly limited, and a known method can be used. The most widely used method is to premix the polycarbonate resin and additives, then put them into an extruder, melt and knead, cool the extruded threads, and cut them with a pelletizer to produce pellet-shaped molding materials The method of doing is mentioned.
  • twin screw extruder As the extruder in the above method, either a single screw extruder or a twin screw extruder can be used, but a twin screw extruder is preferable from the viewpoint of productivity and kneadability.
  • a typical example of such a twin screw extruder is ZSK (trade name, manufactured by Werner & Pfleiderer).
  • Specific examples of similar types include TEX (trade name, manufactured by Nippon Steel Works, Ltd.), TEM (trade name, manufactured by Toshiba Machine Co., Ltd.), KTX (product name, manufactured by Kobe Steel, Ltd.), and the like. Can be mentioned.
  • the extruder one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used.
  • a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing foreign substances mixed in the extrusion raw material in the zone in front of the extruder die part. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.
  • the additive can be independently supplied to the extruder, but it is preferably premixed with the resin raw material as described above.
  • premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer.
  • a more preferable method is to prepare a master agent by mixing a part of the raw material resin and an additive with a high-speed stirrer such as a Henschel mixer, and then use the total amount of the resin raw material and the Nauter mixer to leave such a master agent product. It is a method of mixing with a stirrer which is not high speed.
  • the resin extruded from the extruder is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer and pelletized.
  • a pelletizer and pelletized When it is necessary to reduce the influence of external dust or the like, it is preferable to clean the atmosphere around the extruder.
  • various methods already proposed for polycarbonate resin for optical discs are used to narrow the shape distribution of pellets, further reduce miscuts, and generate fine powder during transportation or transportation. It is preferable to further reduce the amount of bubbles and the bubbles (vacuum bubbles) generated in the strands and pellets.
  • measures such as thread temperature control when cutting with a pelletizer, ionic air blowing during cutting, optimization of the rake angle of the pelletizer, and proper formulation of the release agent, as well as cutting
  • measures such as thread temperature control when cutting with a pelletizer, ionic air blowing during cutting, optimization of the rake angle of the pelletizer, and proper formulation of the release agent, as well as cutting
  • a method of filtering a mixture of pellets and water to separate the pellets from water and miscuts may be used.
  • An example of the measuring method is disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-200421. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver.
  • the miscut amount in the molding material is preferably 10 ppm or less, more preferably 5 ppm or less.
  • the miscut means a granular material finer than a pellet having a desired size that passes through a JIS standard sieve having an opening of 1.0 mm.
  • the shape of the pellet can take a general shape such as a cylinder, a prism, and a sphere, but is more preferably a cylinder (including an elliptic cylinder), and the diameter of such a cylinder is preferably 1.5 to 4 mm, more preferably Is 2 to 3.5 mm.
  • the ratio of the minor axis to the major axis is preferably 60% or more, more preferably 65% or more.
  • the length of the cylinder is preferably 2 to 4 mm, more preferably 2.5 to 3.5 mm.
  • the polycarbonate resin of the present invention can suppress polymer degradation in a basic environment containing an amine.
  • the depolymerization reaction of the polycarbonate with the amine compound proceeds while the amine compound acts on the carbonate bond of the polycarbonate to produce a carbamate ester oligomer as an intermediate. Therefore, in order to suppress the reaction to the carbonate bond by the amine compound, by constituting the structural unit (B) represented by the formula (2) as the main structural unit, the substituent of the aromatic ring can be used for the carbonate bond. It was found to play a role of steric hindrance.
  • the polycarbonate resin of the present invention has a constitutional unit (A) represented by the above formula (1), a constitutional unit (B) represented by the above formula (2), and a constitution represented by the above formula (3). It has been found that by constituting the unit (C) at a specific ratio, the balance of scratch resistance, impact resistance and heat resistance is excellent while maintaining amine resistance.
  • the polycarbonate resin of the present invention preferably has a glass transition temperature of 140 to 160 ° C, more preferably 140 to 155 ° C, and even more preferably 140 to 150 ° C.
  • the glass transition temperature is 140 ° C. or higher, the heat resistance is excellent, and when it is 160 ° C. or lower, the molding processing temperature does not need to be excessively high and molding becomes easy.
  • the polycarbonate resin of the present invention preferably has a Rockwell hardness of 95 or more measured on an M scale according to JIS K7202-2. It is preferable that the Rockwell hardness is 95 or more because of excellent scratch resistance. The upper limit of the Rockwell hardness is 120 or less, and sufficient characteristics are obtained.
  • the polycarbonate resin of the present invention preferably has an impact energy of 25 J or more, more preferably 30 J or more, measured by a high-speed surface impact test measured according to JIS K7211-2. Furthermore, the fracture mode is preferably ductile fracture. An impact energy of 25 J or more is preferable because brittle fracture does not occur and the impact resistance is excellent. The impact energy is 50 J or less and has sufficient characteristics.
  • the polycarbonate resin of the present invention is a hot air type in which the molded product is cut into a flexible urethane foam used for seat cushion material in a shape of 50 mm in length and width and 5 mm in thickness, and enclosed in a glass sealed container, and set at 85 ° C. It is preferable that the appearance of the test piece does not change after being left for 1,000 hours in the dryer.
  • the polyurethane resin is generally produced by reacting a polyol and a polyisocyanate in the presence of a catalyst and, if necessary, a foaming agent, a surfactant, a flame retardant, a crosslinking agent, and the like. It is known that many metal compounds and tertiary amine compounds are used as catalysts for the production of polyurethane resins. These catalysts are often used industrially when used alone or in combination. In the production of polyurethane foams using water, low-boiling organic compounds, or both as blowing agents, among these catalysts, tertiary amine compounds are widely used because of their excellent productivity and moldability. Yes.
  • tertiary amine compounds include conventionally known triethylenediamine, N, N, N ′, N′-tetramethylhexanediamine, N, N, N ′, N′-tetramethylpropanediamine, N , N, N ′, N′-tetramethylethylenediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N ′′, N ′′ -pentamethyldiethylenetriamine, N, N ′, N′-trimethylamino Examples include ethyl piperazine, N, N-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine and the like.
  • the production method for molding a molded product from the polycarbonate resin of the present invention is not particularly limited, and a molding method generally employed for the polycarbonate resin can be arbitrarily adopted.
  • a molding method generally employed for the polycarbonate resin can be arbitrarily adopted.
  • injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used.
  • a molding method using a hot runner method can also be used.
  • the polycarbonate resin of the present invention can be obtained in the form of a sheet or film by a method such as a melt extrusion method or a solution casting method (casting method).
  • a specific method of the melt extrusion method is, for example, that a polycarbonate resin is quantitatively supplied to an extruder, heated and melted, and the molten resin is extruded in a sheet form from a tip of a T die onto a mirror surface roll, and a plurality of rolls.
  • a method is used in which it is taken up while being cooled and cut or wound into an appropriate size when solidified.
  • a specific method of the solution casting method is, for example, casting a solution of polycarbonate resin in methylene chloride (concentration 5% to 40%) from a T-die onto a mirror-polished stainless steel plate, and controlling the temperature stepwise. The sheet is peeled off while passing through the oven and the solvent is removed, followed by cooling and winding.
  • the polycarbonate resin of the present invention can be molded into a laminate. Any method may be used as a method for producing the laminated body, and it is particularly preferable to carry out by a thermocompression bonding method or a coextrusion method. Any method can be adopted as the thermocompression bonding method. For example, a method in which a polycarbonate resin sheet is subjected to thermocompression bonding with a laminating machine or a press machine, a method in which thermocompression bonding is performed immediately after extrusion is preferable, and it is particularly continuous with a polycarbonate resin sheet immediately after extrusion. The method of thermocompression bonding is industrially advantageous.
  • the polycarbonate resin of this invention is excellent in heat resistance, scratch resistance, impact resistance, and amine resistance, it is used as an automotive interior part.
  • Automotive interior parts include interior lighting lamp lenses, display meter covers, meter dials, various switch covers, display covers, heat control panels, instrument panels, center clusters, center panels, room lamp lenses, head-up displays, etc.
  • the automobile interior part of the present invention has the above characteristics, there is an advantage that a polycarbonate resin molded product can be used as it is without requiring a coating treatment.
  • Viscosity average molecular weight of the polycarbonate resin composition is measured and calculated by the following method. First, the polycarbonate resin composition pellets obtained by extrusion were mixed and dissolved with 30 times the weight of methylene chloride, and the soluble component was collected by Celite filtration. Thereafter, the solid obtained after removing the solvent from the obtained solution was sufficiently dried, and the specific viscosity ( ⁇ sp ) at 20 ° C. of the solution was obtained from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride. It was measured. And Mv computed by the following formula was made into the viscosity average molecular weight.
  • composition ratio 40 mg of polycarbonate resin was dissolved in 0.6 ml of deuterated chloroform solution, and 1 H-NMR spectrum was measured with a 400 MHz nuclear magnetic resonance apparatus manufactured by JEOL. The composition ratio of the polycarbonate resin was calculated from the integral ratio.
  • the test piece was a flat plate having a length and width of 100 mm and a thickness of 8 mm.
  • a flexible urethane foam used for automobile seat cushions is cut into a 50mm length and 5mm thickness cutter using a cutter, enclosed in a glass sealed container with a three-stage plate, and set in a hot air dryer set at 85 ° C. The appearance of the test piece after leaving for 1000 hours was visually observed.
  • Example 1 A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 4,555 parts of a 48% aqueous sodium hydroxide solution and 23,088 parts of ion-exchanged water, and 6,6′-dihydroxy-3,3, was added thereto.
  • SBI 3 ', 3'-tetramethyl-1,1'-spirobiindane
  • BPC bisphenol C
  • BPA bisphenol A
  • hydrosulfite 8.06 parts manufactured by Wako Pure Chemical Industries, Ltd.
  • the product is diluted with methylene chloride, washed with water, then added with hydrochloric acid, acidified and washed with water, and further washed with water until the conductivity of the aqueous phase becomes substantially the same as that of ion-exchanged water.
  • a methylene solution was obtained.
  • this solution is passed through a filter having an aperture of 0.3 ⁇ m, and further dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet at the bearing, and the polycarbonate resin is flaked while distilling off methylene chloride.
  • the liquid-containing flakes were pulverized and dried to obtain a polycarbonate copolymer powder.
  • ADK STAB PEP-36A manufactured by ADEKA, phosphorus stabilizer
  • 0 irganox 1076 manufactured by Ciba Specialty Chemicals, hindered phenol antioxidant
  • Riquester EW-400 manufactured by Riken Vitamin, fatty acid ester
  • Chemisorb 79 by Chemipro Kasei, benzotriazole UV absorber
  • the powder was melt-kneaded and extruded while venting with a vented twin-screw extruder [KTX-46, manufactured by Kobe Steel, Ltd.] to obtain polycarbonate resin composition pellets.
  • KTX-46 vented twin-screw extruder
  • Example 2 A polycarbonate resin composition pellet was obtained in the same manner as in Example 1 except that 2,261 parts of BPC, 741 parts of SBI, 1,097 parts of BPA, and 84.2 parts of p-tert-butylphenol were used. The results of evaluation using the pellets are shown in Table 1.
  • Example 3 A polycarbonate resin composition pellet was obtained in the same manner as in Example 1 except that 2,055 parts of BPC, 494 parts of SBI, 1,462 parts of BPA, and 96.2 parts of p-tert-butylphenol were used. The results of evaluation using the pellets are shown in Table 1.
  • Example 4 A polycarbonate resin composition pellet was obtained in the same manner as in Example 1 except that 2,466 parts of BPC, 494 parts of SBI, 1,097 parts of BPA, and 72.2 parts of p-tert-butylphenol were used. The results of evaluation using the pellets are shown in Table 1.
  • Example 5 A polycarbonate resin composition pellet was obtained in the same manner as in Example 1 except that 2,055 parts of BPC, 247 parts of SBI, 1,645 parts of BPA, and 84.2 parts of p-tert-butylphenol were used. The results of evaluation using the pellets are shown in Table 1.
  • Example 6 A polycarbonate resin composition pellet was obtained in the same manner as in Example 1 except that 1,644 parts of BPC, 988 parts of SBI, 1,462 parts of BPA, and 108.2 parts of p-tert-butylphenol were used. The results of evaluation using the pellets are shown in Table 1.
  • Example 7 Polycarbonate resin composition pellets were obtained in the same manner as in Example 1 except that 2,055 parts of BPC, 988 parts of SBI, 1,097 parts of BPA, and 96.2 parts of p-tert-butylphenol were used. The results of evaluation using the pellets are shown in Table 1.
  • Example 8 Polycarbonate resin composition pellets were obtained in the same manner as in Example 1 except that 1,439 parts of BPC, 1,235 parts of SBI, 1,462 parts of BPA, and 91.4 parts of p-tert-butylphenol were used. The results of evaluation using the pellets are shown in Table 1.
  • Example 9 Polycarbonate resin composition pellets were obtained in the same manner as in Example 1, except that 1,850 parts of BPC, 1,235 parts of SBI, 1,097 parts of BPA, and 96.2 parts of p-tert-butylphenol were used. The results of evaluation using the pellets are shown in Table 1.
  • Example 10 In a reactor equipped with a stirrer and a distillation column, 120.8 parts of SBI, 334.6 parts of BPC, 208.6 parts of BPA (a total of 2.61 mol), 588 parts of diphenyl carbonate (2.75 mol) and sodium hydroxide as a catalyst 0.0005 part of tetramethylammonium hydroxide and 0.024 part of tetramethylammonium hydroxide were charged and the atmosphere was replaced with nitrogen. This mixture was dissolved while heating to 180 ° C. Then, the stirrer was rotated and the internal temperature of the reactor was kept at 220 ° C.
  • the pressure in the reactor was reduced from 101.3 kPa to 13.3 kPa over 40 minutes while distilling out the by-produced phenol. Subsequently, a transesterification reaction was performed for 80 minutes while maintaining the pressure in the reactor at 13.3 kPa and further distilling off the phenol.
  • the internal pressure was reduced from 13.3 kPa to 2 kPa as an absolute pressure, and the temperature was further increased to 260 ° C. to remove the distilled phenol out of the system. Furthermore, the temperature was continuously increased, and after the inside of the reactor reached 0.3 Pa or less, the internal pressure was maintained and a polycondensation reaction was performed. The final internal temperature in the reactor was 295 ° C. The polycondensation reaction was terminated when the agitator of the reactor reached a predetermined stirring power. The polymerization reaction time in the reactor was 120 minutes.
  • Example 3 A polycarbonate resin composition pellet was obtained in the same manner as in Example 1 except that 1,932 parts of BPC, 148 parts of SBI, 1,828 parts of BPA, and 84.2 parts of p-tert-butylphenol were used. The results of evaluation using the pellets are shown in Table 2.
  • Example 5 A polycarbonate resin composition pellet was obtained in the same manner as in Example 1 except that 2,877 parts of BPC, 247 parts of SBI, 914 parts of BPA, and 72.2 parts of p-tert-butylphenol were used. The results of evaluation using the pellets are shown in Table 2.
  • Example 8 A polycarbonate resin composition pellet was obtained in the same manner as in Example 1 except that BBI was not used and 494 parts of SBI, 3,290 parts of BPA, and 69.8 parts of p-tert-butylphenol were used. The results of evaluation using the pellets are shown in Table 2.
  • Comparative Example 12 50 parts by weight of the polycarbonate resin of Comparative Example 8 and 50 parts by weight of the polycarbonate resin of Comparative Example 10 were evenly blended, and 0.07 part by weight of ADK STAB PEP-36A (made by ADEKA) was added to 100 parts by weight of the powder.
  • the polycarbonate resin of the present invention does not require a coating treatment, a lamp lens for indoor lighting, a meter cover for display, a meter dial, various switch covers, a display cover, a heat control panel, an instrument panel, a center cluster, a center panel, It can be used for various display devices such as room lamp lenses and head-up displays, automotive interior parts such as protective parts and translucent parts.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne une résine de polycarbonate présentant une excellente résistance à la rayure, une excellente résistance au choc, une excellente résistance thermique et une excellente résistance aux amines. La présente invention porte sur un copolymère de polycarbonate comprenant, en tant que motifs structuraux principaux : (A) un motif structural (A) représenté par la formule (1) [formule 1] (dans la formule (1), R1 et R2 représentent chacun d'une manière indépendante un atome d'hydrogène, un groupe hydrocarboné ayant 1 à 9 atomes de carbone, qui peut comprendre un groupe aromatique, ou un atome d'halogène) ; (B) un motif structural (B) représenté par la formule (2) [formule 2] (dans la formule (2), R3 et R4 représentent chacun d'une manière indépendante un groupe alkyle ayant 1 à 6 atomes de carbone ou un atome d'halogène). X est une liaison simple, un groupe alkylène substitué ou non substitué, un groupe alcanediyle substitué ou non substitué, un atome de soufre ou un atome d'oxygène) ; et (C) un motif structural (C) représenté par la formule (3) [formula 3] (dans la formule (3), W est une liaison simple, un groupe alkylène substitué ou non substitué, un groupe alcanediyle substitué ou non substitué, un atome de soufre ou un atome d'oxygène). Les proportions des motifs structuraux (A), (B) et (C), par rapport à la totalité des motifs structuraux, sont respectivement de 5 à 25 % en moles, de 35 à 60 % en moles et de 30 à 50 % en moles.
PCT/JP2017/046163 2017-01-27 2017-12-22 Copolymère de polycarbonate WO2018139136A1 (fr)

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EP17894197.7A EP3575340B1 (fr) 2017-01-27 2017-12-22 Copolymère de polycarbonate
CN201780084671.2A CN110225934B (zh) 2017-01-27 2017-12-22 聚碳酸酯共聚物
US16/480,019 US20190390006A1 (en) 2017-01-27 2017-12-22 Polycarbonate copolymer

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JP7136668B2 (ja) 2018-11-21 2022-09-13 帝人株式会社 熱可塑性樹脂組成物およびその成形品

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CN110225934A (zh) 2019-09-10
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US20190390006A1 (en) 2019-12-26
EP3575340A1 (fr) 2019-12-04
JP6684931B2 (ja) 2020-04-22
JPWO2018139136A1 (ja) 2019-11-07
EP3575340B1 (fr) 2020-07-15

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